The present invention relates to a new process, particularly simple, convenient and practical, for the preparation of organometallic complexes; more specifically, it relates to a process for the direct synthesis of non-cyclopentadienyl Group IV metal complexes, wherein the metal atom is linked to two sigma ligands selected from the group consisting of linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 arylalkyl radicals, optionally containing Si or Ge atoms.
These complexes are useful as catalyst components, e.g. in the polymerization, oligomerization and hydrogenation of olefins, in association with alumoxanes and/or compounds able to form alkylmetal cations.
Homogeneous catalytic systems based on Group IV metal complexes containing chelating diamido or dialkoxide ligand systems are well known in the state of the art and their use in olefin polymerization reactions has recently received increasing attention. These complexes are usually employed as dihalide or dialkyl derivatives, in association with suitable cocatalysts, such as alumoxanes and borate salts; dichloride metal complexes are the most commonly used derivatives.
Dialkyl metal complexes are synthesized by passing through the corresponding dihalide derivatives, which are hydrocarbylated by ligand exchange with an appropriate hydrocarbylating agent to the target products; total yields are generally unsatisfactory and the following process steps are required:
(1) preparing the dihalide metal coordination complex by reacting a suitable ligand, usually silylated or derivatized with suitable leaving groups, with MX4 (usually TiCl4 or ZrCl4);
(2) converting the dihalide complex obtained in step (1) into the corresponding dialkyl complex, by substitution of the halogens linked to the metal atom with the desired alkyl or aryl groups, by means of an alkylating agent such as alkyllithium, dialkylmagnesium or the corresponding Grignard reagent.
Therefore, dialkyl complexes can not be expediently synthesized by the existing methodology. For instance, J. Okuda et al. (Chem. Ber. 128: 221-227, 1995) described the preparation of a class of titanium complexes containing bidentate bis(phenoxy) ligands; dimethyl complexes were synthesized by the reaction of the corresponding dichloride derivatives with Grignard reagents, such as methylmagnesium bromide, at xe2x88x9278xc2x0 C.
D. McConville and coworkers (Journal of Molecular Catalysis A: Chemical 128:201-214, 1998) described the reaction of RHN(CH2)3NHR (wherein R is aryl) with 2 equivalents of BuLi, at xe2x88x9278xc2x0 C., followed by 2 equivalents of ClSiMe3, at 0xc2x0 C., to produce the silylated diamine ligand R(Me3Si)N(CH2)3N(SiMe3)R; this diamine ligand was then treated with TiCl4 to yield the dichloride complex [RN(CH2)3NR]TiCl2 in unsatisfactory yields. Without the previous silylation of said diamine ligand, the reaction of the ligand dilithium derivative with TiCl4(THF)2 gave very low yields ( less than 10%). The dichloride complex [RN(CH2)3NR]TiCl2 was then reacted with 2 equivalents of MeMgBr, to give the dimethyl derivative [RN(CH2)3NR]TiMe2. These complexes are active catalysts for the polymerization of xcex1-olefins, and in particular 1-hexene.
With regard to alternative synthetic strategies for the production of metal diarnido complexes, the M(NR2)4 precursor amine elimination approach has provided in general a more efficient preparation than conventional salt elimination synthetic routes (see R. Schrock et al., Organometallics, 17:4795-4812, 1998).
However, this route usually leads to a myriad of undesired products and, for subsequent catalysis, it is critical that the amido complexes be converted to dichloride or dialkyl polymerization catalyst precursors, because amido-derived catalysts are significantly less active than chloride or alkyl-derived catalysts.
More specifically, as reported by R. Schrock in the cited reference, the reaction between M(NMe2)4 and a diamine ligand produced the corresponding M(NMe2)2 complex, which was then reacted with an excess of Me3SiCl in ether to form the MCl2 complex; finally, the dichloride species was alkylated by using a Grignard reagent to afford the corresponding dialkyl complex, in unsatisfactory final total yields.
Also in this case, in order to achieve the desired dialkyl metal complex, it is necessary to pass through the metal dihalide derivative, thus requiring numerous reaction steps and lowering total reaction yields. Therefore, the prior art processes for producing metal complexes having hydrocarbon sigma ligands bonded to the central metal atom are inadequate for a commercially viable and practical production of said complexes, for use as catalyst components in olefin polymerization; it is felt the need for a simpler and more convenient and practical method to produce these complexes in satisfactory yields.
The Applicant has now unexpectedly found a new process for the preparation of organometallic complexes of formula (I):
(A)(ZR1m)n(Axe2x80x2)MLpLxe2x80x2qxe2x80x83xe2x80x83(I)
wherein:
(ZR1m)n is a C1-C50 divalent group bridging A and Axe2x80x2, Z being C, Si, Ge, N, P, O or S; the R1 groups, equal or different from each other, are hydrogen or linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl groups; two or more R1 may form together one or more saturated, unsaturated or aromatic rings;
m is 0, 1 or 2, and more specifically it is 0 when Z is O or S, it is 1 when Z is N or P, and it is 2 when Z is C, Si or Ge;
n is an integer ranging from 1 to 8;
A and Axe2x80x2, the same or different from each other, are divalent anionic groups selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and xe2x80x94N(R2)xe2x80x94, wherein R2 is hydrogen, a linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl, optionally containing one or more atoms belonging to Groups 13-17 of the Periodic Table;
M is a transition metal belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups of the Periodic Table of the Elements (IUPAC version);
the substituents L, the same or different from each other, are monoanionic sigma ligands selected from the group consisting of linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 arylalkyl groups, optionally containing one or more Si or Ge atoms; preferably, the substituents L are the same;
the substituents Lxe2x80x2, the same or different from each other, are halogens or xe2x80x94OR3, wherein R3 is hydrogen or a linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl group;
p is an integer ranging from 1 to 3; q is an integer ranging from 0 to 2, p+q being equal to the oxidation state of the metal M minus 2, and p+q being xe2x89xa63;
said process comprising the following steps:
(1) reacting a ligand of formula (Hxe2x80x94A)(ZR1m)n(Axe2x80x2xe2x80x94H) with about (2+p) molar equivalents of a compound of formula LjB or LMgLxe2x80x2, wherein A, Axe2x80x2, Z, R1, m, n, p, L and Lxe2x80x2 have the meaning reported above; B is an alkaline or alkaline-earth metal; and j is 1 or 2, j being equal to 1 when B is an alkaline metal, and j being equal to 2 when B is an alkaline-earth metal; and
(2) reacting the product obtained from step (1) with about 1 molar equivalent of a compound of formula MLxe2x80x2s, wherein M and Lxe2x80x2 have the meaning reported above; s is an integer corresponding to the oxidation state of the metal and ranges from 3 to 6.
The process of the invention allows organometallic complexes to be obtained, wherein the metal bears one or more sigma-bonded hydrocarbon substituents, in a simple, rapid and economic way, leading to the desired products in one reactor, starting from the suitable ligands. Moreover, said process leads to final yields much higher than the ones obtainable with the procedures known in the state of the art, therefore allowing a convenient industrial exploitation of the above organometallic complexes as catalyst components in the polymerization of olefins. In the complexes of formula (I), the divalent bridge (ZR1m)n is preferably selected from the group consisting of xe2x80x94CR12xe2x80x94, xe2x80x94CR12xe2x80x94SiR12xe2x80x94, 
R1 having the meaning reported above; more preferably, said divalent bridge is xe2x80x94Si(CH3)2xe2x80x94, xe2x80x94SiPh2xe2x80x94, xe2x80x94Si(CH3)2xe2x80x94Si(CH3)2xe2x80x94, xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, xe2x80x94(CH2)3xe2x80x94 or xe2x80x94C(CH3)2xe2x80x94.
The variable m is 0, 1 or 2; the variable n ranges from 1 to 8 and, when n greater than 1, the atoms Z can be different from each other, such as for instance in divalent bridges xe2x80x94CH2xe2x80x94Oxe2x80x94, xe2x80x94CH2xe2x80x94Sxe2x80x94 and xe2x80x94CH2xe2x80x94Si(CH3)2xe2x80x94 (when n=2).
According to preferred embodiments of the process of the invention, in said divalent bridge (ZR1m)n, two or more R1 groups form together one or more saturated, unsaturated or aromatic rings, optionally condensed.
Examples of preferred divalent bridges are the following: 
wherein the R1 groups have the meaning reported above.
The groups A and Axe2x80x2, the same or different from each other, are selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and xe2x80x94N(R2)xe2x80x94, wherein R2 is defined as above; said groups A and Axe2x80x2 are preferably the same and are preferably xe2x80x94N(R2)xe2x80x94 or xe2x80x94Oxe2x80x94, i.e. an amido or an alkoxy group, wherein R2 is a linear or branched C1-C10 alkyl, a C7-C15 alkylaryl or a C7-C15 arylalkyl, optionally containing one or more heteroatoms belonging to Groups 13-17 of the Periodic Table, such as B, Si, GE, O, S, N, P, Cl and Br; even more preferably, R2 is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers of these alkyl radicals, norbomyl, benzyl, phenyl, 2,6-dialkyl-phenyl (such as 2,6-dimethyl-phenyl and 2,6,-diisopropyl-phenyl), 2,4,6-trialkyl-phenyl (such as 2,4,6-trimethyl-phenyl), trialkyl-silyl (such as trimethyl-silyl and triisopropyl-silyl) and diaryl-boryl (such as dimesityl-boryl).
The group R2 may optionally contain xe2x80x94ORxe2x80x2, SRxe2x80x2, xe2x80x94NRxe2x80x22 or xe2x80x94PRxe2x80x22 groups, wherein Rxe2x80x2 is a C1-C10 alkyl group; the presence of this addition weak neutral donor site within the chelating cyclopentadienyl ligand framework may give rise to a tridentate ligand complex; more preferably, the donor group is xe2x80x94OMe, xe2x80x94OEt or xe2x80x94NMe2.
The metal M is preferably Ti, Zr or Hf, and more preferably Ti.
The substituents L are preferably the same and are preferably selected from the group consisting of C1-C7 alkyl, C6-C14 aryl and C7-C14 arylalkyl groups, optionally containing one or more Si or Ge atoms; even more preferably, the substituents L are selected from the group consisting of methyl, ethyl, n-butyl, sec-butyl, phenyl, benzyl and xe2x80x94CH2Si(CH3)3. According to a favorite embodiment of the invention, L is methyl.
The substituents Lxe2x80x2 are preferably Cl, Br or OR3, wherein R3 has the meaning reported above, and more preferably it is a C1-C6 alkyl or a C6-C10 aryl; even more preferably, Lxe2x80x2 is selected from the group consisting of Cl, Br, xe2x80x94OMe, xe2x80x94OEt, xe2x80x94OPr, xe2x80x94OBu and xe2x80x94OBz.
The process according to the present invention comprises the following steps:
(1) reacting a ligand of formula (Hxe2x80x94A)(ZR1m)n(Axe2x80x2xe2x80x94H) with about (2+p) molar equivalents of a compound of formula LjB or LMgLxe2x80x2, wherein A, Axe2x80x2, Z, R1, m, n, p, L and Lxe2x80x2 have the meaning reported above; B is an alkaline or alkaline-earth metal; and j is 1 or 2, j being equal to 1 when B is an alkaline metal, and j being equal to 2 when B is an alkaline-earth metal; and
(2) reacting the product obtained from step (1) with about 1 molar equivalent of a compound of formula MLxe2x80x2s, wherein M and Lxe2x80x2 have the meaning reported above, and s is an integer corresponding to the oxidation state of the metal and ranges from 3 to 6.
The organometallic complexes of formula (I) can be finally isolated from the reaction mixture obtained in step (2) and optionally purified according to standard procedures. Said process allows to obtain the complexes of formula (I) in very high yields, by means of a very practical and convenient one-pot reaction.
The ligand of formula (Hxe2x80x94A)(ZR1m)n(Axe2x80x2xe2x80x94H), wherein A, Axe2x80x2, Z, R1, m and n have the meaning reported above, may be synthesized according to procedures known in the state of the art. For instance, suitable bridged bis-amine ligands may be prepared as described in WO 96/27439. Moreover, suitable bridged bis-hydroxy ligands may be prepared as described in EP-A-241,560 (see ligands corresponding to formulae (I), (II), (III), (IV), (V) and (VI)). In the reactant MLxe2x80x2s, the metal M is preferably Ti, Zr or Hf, and the substituents Lxe2x80x2 are preferably the same and are selected from the group consisting of xe2x80x94Cl, xe2x80x94Br, xe2x80x94OMe, xe2x80x94OEt, xe2x80x94OPr, xe2x80x94OBu and xe2x80x94OBz; the variable s ranges from 3 to 6 and corresponds to the oxidation state of the metal M. Said reactant is preferably selected from the group consisting of TiCl4, ZrCl4, HfCl4, ScCl3, YCl3, NbCl5, Ti(OEt)4, Ti(OPr)4, Ti(OBz)4, Zr(OEt)4, Zr(OPr)4, Zr(OBz)4, Zr(OEt)3Cl, Hf(OEt)4, Hf(OPr)4 and Hf(OBz)4; this reactant can be used even in the form of a stabilized derivative, such as an etherate complex of MLxe2x80x2s, easily available on the market. LjB and LMgLxe2x80x2 are alkylating agents, wherein L is preferably a C1-C7 alkyl group, a C6-C14 aryl group or a C7-C14 arylalkyl group, optionally substituted with Si or Ge, and more preferably L is selected from the group consisting of methyl, ethyl, n-butyl, sec-butyl, phenyl, benzyl and xe2x80x94CH2Si(CH3)3; even more preferably, L is methyl.
In the compound LjB, B is an alkaline or alkaline-earth metal, and preferably Li or Mg; j can be 1 or 2, as already reported.
The compound LMgLxe2x80x2 is a Grignard reagent, wherein Mg is magnesium and L and Lxe2x80x2 have the meanings reported above; Lxe2x80x2 is preferably Cl or Br.
According to a preferred embodiment of the process of the invention, said alkylating agent is methyllithium.
The molar ratio of the compound of formula LjB or LMgLxe2x80x2 to the ligand of formula (Hxe2x80x94A)(ZR1m)n(Axe2x80x2xe2x80x94H) can vary within wide limits; an improved process for obtaining dihydrocarbyl organometallic complexes of formula (I), wherein p=2 and q=0, is obtained at a ratio of about 4:1 and higher; an improved process for obtaining monohydrocarbyl complexes of formula (I), wherein p=1 and q=1, is obtained at a ratio of about 3:1.
The molar ratio of the compound of formula MLxe2x80x2s to the ligand of formula (Hxe2x80x94A)(ZR1m)n(Axe2x80x2xe2x80x94H) is preferably about 1:1.
According to a preferred embodiment, the process of the invention is carried out in an aprotic solvent, either polar or a polar; said aprotic solvent is preferably an aromatic or aliphatic hydrocarbon or an ether, and more preferably it is selected from the group consisting of benzene, toluene, pentane, hexane, heptane, cyclohexane, diethylether, tetrahydrofuran and mixtures thereof.
According to a preferred embodiment of the process of the invention, in step (1), said ligand (Hxe2x80x94A)(ZR1m)n(Axe2x80x2xe2x80x94H) is previously dissolved in an aprotic solvent and to the resulting solution is added the alkylating agent LjB or LMgLxe2x80x2; this addition is preferably carried out at a temperature ranging from xe2x88x9280xc2x0 C. to +50xc2x0 C., and more preferably from xe2x88x9250xc2x0 C. to +30xc2x0 C. The alkylating agent is preferably added in the form of a solution in one of the above mentioned aprotic solvents.
The thus obtained reaction mixture is then allowed to react, under stirring, at a temperature preferably comprised between xe2x88x9280xc2x0 C. and +50xc2x0 C., more preferably between xe2x88x9250xc2x0 C. and +30xc2x0 C., and even more preferably at room temperature.
Before the reaction with MLxe2x80x2s in step (2), the mixture obtained from step (1) has preferably a temperature ranging from xe2x88x9280xc2x0 C. to +50xc2x0 C., and more preferably it is cooled to a temperature ranging from xe2x88x9250xc2x0 C. to room temperature; then, MLxe2x80x2s is quickly added to the cooled mixture, in the form of a solution in one of the above mentioned aprotic solvents, preferably pentane.
The reaction mixture is then allowed to react at a temperature comprised between xe2x88x9280xc2x0 C. and +50xc2x0 C., more preferably between xe2x88x9250xc2x0 C. and +30xc2x0 C., and even more preferably at room temperature. The thus obtained organometallic complexes of formula (I) can be isolated according to procedures known in the state of the art.
These organometallic complexes are useful in addition oligomerization and polymerization processes wherein, in association with an activating cocatalyst, they are contacted with one or more addition polymerizable monomers.
Addition polymerizable monomers include ethylenically unsaturated monomers, conjugated or non-conjugated dienes and polyenes. The above organometallic complexes are particularly useful in homo and co-polymerization of xcex1-olefins of formula CH2xe2x95x90CHR, wherein R is hydrogen or a C1-C20 alkyl, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene; preferably said xcex1-olefin is 1-hexene.
As reported above, the organometallic complexes obtained with the process of the invention form suitable polymerization catalytic systems in association with activating cocatalysts, such as alumoxanes, aluminium alkyls, aluminium halides, aluminium alkylhalides, Lewis acids, ammonium salts, non-interfering oxidizing agents and mixtures thereof.
Preferably the ratio of the organometallic complex and the cocatalyst on a molar basis is from about 1:0.1 to about 1:10,000, and more preferably from 1:1 to 1:1,000.
Suitable activating cocatalysts are linear alumoxanes having the following formula: 
wherein the substituents R4, the same or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 arylalkyl radicals, optionally containing Si and Ge atoms, and y ranges from 0 to 40; R4 is preferably methyl, ethyl, isobutyl or 2,4,4-trimethyl-pentyl; or cyclic alumoxanes having the following formula: 
wherein R4 has the meaning herein described and y is an integer ranging from 2 to 40. Examples of alumoxanes suitable as activating cocatalysts in the catalysts according to the present invention are methylalumoxane (MAO), tetra-isobutyl-alumoxane (TIBAO), tetra-2,4,4-trimethylpentylalumoxane (TIOAO) and tetra-2-methyl-pentylalumoxane. Mixtures of different alumoxanes can also be used.
Suitable activating cocatalysts are also the products of the reaction between water and an organometallic aluminum compound, preferably of formula AlR43 or Al2R46, wherein R4 has the meaning reported above. Particularly suitable are the organometallic aluminum compounds of formula (II) described in EP-A-575,875, those of formula (II) described in WO 96/02580, those described in WO 99/21899 and in the European app. no. 99203110.4. Mixtures of different organometallic aluminum compounds can also be used.
Further suitable activating cocatalysts are those compounds capable of forming an alkylmetal cation; preferably, said compounds have formula Y+Zxe2x88x92, wherein Y+ is a Bronsted acid capable of donating a proton and of reacting irreversibly with a substituent X of the compound of formula (I), and Zxe2x88x92 is a compatible non-coordinating anion, capable of stabilizing the active catalytic species which result from the reaction of the two compounds, and which is sufficiently labile to be displaceable by an olefinic substrate. Preferably, the Zxe2x88x92 anion comprises one or more boron atoms. More preferably, the anion Zxe2x88x92 is an anion of formula BAr4(xe2x88x92), wherein the Ar substituents, the same or different from each other, are aryl radicals such as phenyl, pentafluorophenyl, bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl-borate is particularly preferred. Moreover, compounds of formula BAr3 can be conveniently used.
The polymerization process may be carried out in liquid phase, optionally in the presence of an inert hydrocarbon solvent either aromatic (e.g. toluene) or aliphatic (e.g. propane, hexane, heptane, isobutane, cyclohexane or 2,2,4-trimethylpentane), or in the gas phase.
The polymerization is conducted according to known techniques for Ziegler-Natta or Kaminsky-Sinn type polymerization, at a temperature generally ranging from about xe2x88x9230xc2x0 C. to about 250xc2x0 C., and preferably from 20 to 150xc2x0 C., at reduced, elevated or atmospheric pressures. The molecular weight of the polymers can be varied by changing the type or the concentration of the catalytic components or by using molecular weight regulators, for example hydrogen. The catalyst may be used as it is, or supported on a suitable organic or inorganic support, to provide a heterogeneous supported catalyst.
The following examples are given for illustrative and not limiting purposes.
General Procedures and Characterizations
All operations were performed under nitrogen by using conventional Schlenk-line techniques. Solvents were purified by degassing with nitrogen and passing over activated alumina and subsequently stored under nitrogen. MeLi (Acros) and TiCl4 were used as received.
The compounds were analyzed by 1H-NMR by using a AC200 Bruker spectrometer, operating at 200.13 MHz. All NMR solvents were dried over P4O10 and distilled before use. Preparation of the samples was carried out under nitrogen, using standard inert atmosphere techniques.